Certain water-soluble high molal oxyalkylated esters and method of making same



Patented May 8,

2,315,529 cen'mm WATER-SOLUBLE men MOLAL OXYALKYLATED ESTER/S AND .METHOD OF MAKING SAME Melvin Dc Groote, University City, and Bernhard Keiser, Webster Groves, Mo., asslgnors to Pet- 'rolite Corporation, Ltd., Wilmington, DeL, a

corporation of Delaware I No Drawing. Original application March 21,

1941, Serial No. 384,598. Divided-and this ap-. plication' August 14, 1942, Serial No. 454,876

13 Claims. (c1. act-404.5)

This invention relates to a new chemical product or compound, our present application being a division of our co'-pending application Serial No. 384,598, filed March 21, 1941, which subsequently matured as U. S. Patent No. 2,296,600, dated September 22, 1942. I

One object of our present invention is to provide a new material, compound, or composition of'matter, that is capable of use for various purposes, and particularly adapted for use as a demulsifier in the resolution of crude oil emulsions.

Another object of ourinvention is to provide a practicable method for manufacturing said new material, compound or composition of matter.

The new chemicalcompound 'or composition of matter which constitutes our present invention is exemplified by the acid; or preferably, neutral ester derived by complete esterification of one mole of a polyalkylene glycol of the kind hereinafter described, with two moles of a fractional ester derived from a hydroxylated material of the quantitie may be indicated by the following fori The polyethylene glycol maybe characterized by materials of the kind such as heptaethylene glycol,- octaethylene glycol, nonaethylene glycol, decaethylene glycol, to and including heptadeca ethylene glycol. For. convenience, these polyethylene glycols may be indicated by the. following formula:

OH(C2H40) mH in which m varies from '7 through 17.

Instead of polyethylene glycols, one may use polypropylene glycols or polybutylene glycols. Thus, for convenience, in the broadest aspect, the polyalkylene glycols employed may be indicated by'the following formula: I

in which m has its previous significance and n represents a numeral varying from 2 to 4.

Thus, the bulk of the materials herein contemplated, particularly for use as demulsiflers, may

I be indicated within certain variations, as hereinafter stated, by the neutral ester derived by esterification of one mole of a glycol of the kind above described, with two moles of a fractional 5 ester of the kind previously indicated. The formation of the compound may be indicated by the following reaction, although obviously, it is immaterial what particular procedureisemployed to produce the particular chemical compound or product:

usually concerned largely with convenience of manufacture of the finished ester, and also of the price of the reactants. -Generally speaking, the .higher the temperature employed, the easier it is to obtain large yields of the esterified product. Although oxalic acid is comparatively ,cheap, it decomposes somewhat; readily at slightly above the boiling point of water. For this reason, it is more desirable to use an acid-which is more resistant to pyrolysis. Similarly, when.a polydride, such anhydride is apt to produce the ester with greater ease than the acid itself. For this reason, maleic anhydride is "particularly adaptable; and also, everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis. Succinic acid or the anhydride has many of the attractive qualities ofmaleic anhydride; and this 46 is also true of adipic acid. For purposesofbrevalthough it is understood that any other suitable polybasic acid may be employed. Furthermore, for purposes of convenience, reference is made to the use of polyethylene glycols. As has been previously indicated, such glycols can be replaced by suitable polypropylene -or polybutylene compounds.

As far as the range of 'oxyalkylated compounds employed as reactants is concerned, it is our prefbasic acid is available in .the form of an anhy-' ity, the bulk of the compounds hereinafter illus- I trated will refer to the use of maleic anhydride,

eren'ce to employ those having' approximately the presence of a hydroxy hydrocarbon radical 8-1-7 oxyalkylene groups, particularly 8-12 oxyv ethylene groups. The preference to use the oxyethylated compounds is due largely to the fact that they are commercially available, and particularly so in two desirable. forms. The most desirable form is the so-called nonaethylene glycol,

which, although consisting largely of nonaethylene glycol, may contain small amounts of heptaethylene and octaethylene glycols, and possibly minor percentages of the higher homologs. Such glycols represent the upper range of distillable glycols; and they may be conveniently referred to as jupper distillable' ethylene glycols. There is no particularly good procedure for making a sharper separation on a commercial scale; and it is understood that mixtures of one or' more of the glycols may be employed, as well'as a single glycol. As pointed out, it is particularly preferred to employ nonaethylene glycol as commercially available, although it is understood that this product contain other homologs as indicated.

Substantially as desirable as the. upper distillable polyethylene glycols, are the lower nondistillable polyethylene glycols. These materials are available in the form of a Waxy water-soluble material, and the general range may vary somewhat froni decato tetradecaethylene glycol. As

is well understood, the methodof producing such glycols would cause some higher homologs to b formed; and thus, even in this instance theremay be present some oxyethylene glycols within the higher range above indicated. One need not point out that these particular compounds consist of mixtures, and that in some instances, particularly desirable'esters are obtained by making mixtures :of the liquid nonaethylene glycol with the soft, waxy, lower non-distillable polyethylene For the sake of convenience, reference glycols. in the examples will be to nonaethyle'ie glycol: and calculations will be based on a theoretical molecular weight of 414-. Actually, in manufac ture themolecular weight of the glycol employed. whether a higher distillable polyethylene glycol or'a lower non-distillablepolyethylene glycol, or a mixturefof the same, should be determined and reaction conducted on the basis of such determi'-.

nation, particularly in conjunction with the hydroxyl or acetyl value.

It has been previously pointed out that it is immaterial how the compounds herein contemplated are manufactured, although we have found it most desirable to react the selected glycol or mixtures of 'glycols with maleic anhydride in a ratio of two moles of the anhydride for one moleof the glycol. Under such circumstances, we have. found little -tendency to form longer chain polymers; andin fact, the product of reaction, if conducted at' reasonably low temperatures, appears to be largely monomeric. For convenience. such intermediate product may then x and *ethylene'oxide, yields a material of the for-- be considered as a dibasicor polybasic acid. One I mole ofthe intermediate; so obtained is then re acted with two moles of the alcoholic materia of the kind subsequently described,

It is to be noted, however, that if one prepares y a fractional acidic ester, then if two moles of the. fractional acidic ester are {reacted with one mole,

of the polyethylene glycol, there is no possibility for the formation of polymeric typesof esterification products under ordinary conditions.

The hydroxylated compounds employed as reactants in the manufacture of the present compounds are substituted amides characterized by.

containing at least one alcoholic hydroxyl radical as a substituent for an amino hydrogen atom.

Such hydroxylated amides are of the kind in which the acyl radical is derived from'a detergent-forming acid.

v Detergent-forming acids are monocarboxy acids having more than 8 and not over 32 carbon apt to contain from 12-14 carbon atoms as a lower limit, to 18-22 carbon atoms as an upper limit. Oxidized wax acids may contain as many as 32 carbon atoms.

It is well known, of course, that amides may be obtained by reaction between long chain carboxy acids and monoalk-ylolamines, such as monoethanolamine, monopropanolamine, monobutanolamine, etc. The manufacture of such chemical compounds, particularly where derived from higher fatty acids, is described in British Patent No. 450,672, dated July 17, 1936, to Orelup. Another procedurewhich has been employed for the same purpose is to react the monoalkylolamine with the acyl chloride derived from a suitable carboxy acid. Still another method employs the use of an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, and the 7 like, in connectionwith an amide.

4 Reference is made to U. S. Patent No. 2,002,613, dated May 28, 1935, to Orthner and Keppler. This latter method for producing oxy-amides is not limited' to the use of alkylolamines, such as monoalkylol-. amines, dialkylolamines, or the like, as the raw material, but may employ alkylamines, aryl-' amines, aralkylamines, alicyclic amines, etc., sov

as to obtain hydroxylated derivatives. Naturally, the methods employing monoalkylamines, and particularly" the process in which acyl chlorides are employed, may also use such materials as diethanolamine, dipropanolamine, dibutanolam ine,

.and the like. Amides so obtained may have as many as six hydroxyl radicals in the amino-hydrogen position.

It is known, of course, that when primary and secondary amines are reacted with various alkylene oxides, one may obtain hydroxyethyl alkylamines, hydroxypropyl alkylamines, etc. Thereaction, for example; between a primary amine mula type HQ.CH2.CH2.NHR. Such amines may be reacted withdetergent-forming carboxy acids to give suitable amides.

Briefly, then, in a practical wayamides can be derived from detergent-forming acids or some derivative, usually an ester. often more suitable reactants foramidification than the acids themselves. As to themanufacture of esters, see the following United States patents, towit: No. 1,160,595, dated No'v.'16, 1915,-

e to Gruter et al.; No. 2,221,674, dated Nov. 12, 1940.

to'Ellis; and No. 2,177,407, dated-Oct, '24, 1939, to

Hansley.

Indeed,'-esters are j contains not'over 7 carbon atoms.

where R'" is a hydrocarbon radical.

' See also Organic 88, 1930. I

As to the procedure for the manufacture of Syntheses, volume X. P ge amides or substituted amides, see the following- United States patents: No. 2,058,013, dated Oct.

20, 1936, to Henke et $1.; No. 2,013,108, dated Sept. 3, 1935, Reppe et al.; No. 1,475,477, dated Nov. 2'7, 1923, Ellis; and No. 1,954,433, dated Apr.

10, 1934, to Thomas et a1.

In.any event, suitable amideshaving been b-v tained, either from the acids, esters, or any other derivative, they may then be treated with ethylene' oxide, propylene oxide, butylene oxide, glycid, or the like. Similarly, instead of obtaining the amides, one may obtain the substituted amides, i. e., the derivatives of amylamine, cyclohexylamine, aniline, benzylamine, or the like, particularly the substituted amides, in which the hydro carbon radical replacing an amino hydrogen atom stituted amides then can be treated with oxyalkylating agents in the same manner previously described in connection with the amides.

Such subacids, and especiallyunsaturated fatty acids, such Another suitable procedure is simply to react the selectedester or acid or other suitable derivative, with a hydroxylated primary amine, such as monoethanolamine, monopropanolamine, monobuta'nolamine, monoglycerylamine, tris(hydroxymethyl) aminomethane,- and the like. Such reactants readily yield the hydroxylated amide of the kind contemplated.

. Reactions can also be conducted with secondary hydroxylated amines of the kind exemplified by diethanolamine, dipropanolamine, diglycerylamine, etc. When this latter type of reactant is employed, one is more apt to obtain a significant RCON onion c-cmon onion i Our preferred amides are derivatives 'of fatty as oleic acid, ricinolelc acid, etc.

Acidic intermediate product, Example 1 One pound mole of nonaethylene glycol is reacted with two pound moles of maleic anhydride so as to form nonaethylene glycol dihydrogen dimaleate, a compound of the following structure:

HOOC-.CH4.COO(C2H4O)BC2H4.OPC.C2H4.COOH

Acidic intermediate producLEzample 2 A mixture of lower non-distillable polyethylene glycols, representing approximately decato tetra'decaethylene glycol, is substituted for nonaethyleneglycol in the preceding example.

Acidic intermediate product, Example 3 A +50 mixture of nonaethylene glycol and lower non-distillable polyethylene glycols of the kind described in the previous examme is sub- I stitute'd for nonaethylene glycol in Example 1.

amount of esterified compound along with the amide derivative.

any event, one can readily obtain amides of the kind indicated by the following formulae in which RC0 is the acyl radical of a detergent-forming noon The same also applies when I material of the type exemplified by ethyl ethanolamine, phenyl ethanolamine, cyclohexyl ethanolamine, etc., are employed for amidification; In

Acidic intermediate product, Eramplc 4 Adipic acid is substituted for maleic anhydride' in Examples 1-3, preceding.

Acidic intermediate product, Example 5 Oxalic acid is substituted for maleic anhydride in Examples 1-3, preceding.

Acidic intermediate product, Example 6 Citric acid is substituted for maleic anhydride in Examples 1-3, preceding.

Acidic intermediate producLEaample 7 Succinic anhydride is substituted for maleic anhydride in Examples 1-3, preceding.

' Composition of matter, Example One pound mole of the intermediate product of v the kind described in Intermediate product-Examples 1, 2 and 3,'above, is reacted with two pound moles of the oleic acid amide or mono-. ethanolamine, until substantially all dibasic carboxyl acidity has disappeared. Time of reaction may vary from a few hours to as..mucli as 20 hours.

Composition of matter, Example 2 I Ricinoleic acid amide'ot monoethanolamine is substituted for the oleic acid-amide of monoethanolamine in the preceding example.

and te'aseed oil fatty acids is substituted for the i QCompo'siti on of matter, Example 3 The amidederived from monoethanolamine and cocoanut oil fatty acids is substituted for the 'oleic,ac id amide of mcnoethanolamine in Composition of matter, Example 1.

" Composition r matter, Example 4' The amide derived from monoetha'nolamine' oleic acid amide ofmonoethanolamine in Composition of matter; Example 1.

Composition of matter, Example 5 Y H The substituted amide derived from methanolamine. which may be obtained by means or ethylene oxide and the unsubstituted amide, is substituted for the corresponding monoethanolamine derivativein' the preceding four examples.

Composition matter, Example 6 The amide derived from tris(hydroxymethyl) aminomethane is substituted for the amide derived from monoethanolamine in Composition 0 matter, Examples 14, inclusive.

Composition of matter, Example 7 The corresponding amide derived from monoglycerylamine is substituted for the amide derived from monoethanolamine in Composition of matter, Examples 1-4, inclusive.

Composition of matter, Example 8 Amides derived from diglycerylamine, and preferably, obtained by the action of glycidol on the amide, are substituted for the corresponding, j monoethanolamine amides in Composition of matter, Examples 1-4, inclusive.

Composition of matter, Example 9 InComp'osltion of matter, Examples 1-8, pre

\ ceding, any residual acidity present isremoved by cautiously adding a dilute solution of ammonium hydroxide until the resultant product gives a clear, limpid solution in water, particularly in 1 dilute form.

2,375,529 Q substituted for that in Intermediate product, Ex-

Composition of matter,- Example 10 In Composition of matter, Examples 1-8, preceding, any residual acidity present is removed by 1 cautiously adding a dilute solution 0! triethanolamine until the resultant product gives a clear,

, limpid solution in 7 form.

water, particularly in dilute Composition of matter, Example 11 In'Composition of matter, Examples 1-8, pre-' ceding, any residual acidity present i removed by cautiously adding a dilute solution oftris(hydroxymethyl) aminomethane until the resultant product gives a clear, limpid solution in water,

' particularly in dilute form.

Composition of matter, Example 12 The same procedure is followed as in Composi- ;tion of matter, Examples 1-11, inclusive, except that an intermediate product of the kind exem- 1 plified by Intermediate product, Example 4, is j substituted for that in Intermediate product, Examples 1, 2 and 3.

Composition of matter, Example 13 The same procedure is followed as in Composi tion of matter, Examples 1-11, inclusive, except that an intermediate product of the kind exemplified by Intermediate product, Example 5, is substituted for that in Intermediate product, Examples 1, 2 and 3.

Composition of matter, Example .14 The same procedure is followed as in Composi- 1 tion of matter, Examples 1-11, inclusive, except that an intermediate product of the kind exemplified 'by Intermediate product, Example 6, is substituted forthat in Intermediate product, Ex amples 1, 2 and 3.,

' Composition of matter, Example, The same procedure is followed as in Composition of matter, Examples 1-11, inclusive, except that an intermediate product of the kind exemplifledby Intermediate product, Example 7, is

manner:

amples 1, 2 and 3.

It is to be noted that this second step is anesterification reaction, and the same procedure is employed as suggested above in the preparation of the intermediate product. Needless to say, any

particular method may be used to produce the desired compounds of the kind indicated. In some instances, it may be desirable to conductthe esterification reaction in the presence of a nonvolatile inert solvent which simply acts as-a 'diluent or viscosity reducer.

In the preceding examples, attention has been directed primarily'to the monomeric form, or at least, to the form in which the bifunctional alcohol, i. e, a glycol, and the polyfunctional acid,

usually a bifunctional compound, react'to give a chain type compound in which the adjacent acid and glycol nucleus occur as a structural unit. For

instance, in the monomeric form this may be indicated in the following manner:

/ acid glycol acid uct which might, be indicated in the acid glycol f, acid glycol acid Similarly, three :moles of the glycol and four moles of the acid would give a combination which may be indicated thus: 3

acid glycol acid glycol acid glycol acid Another way of stating the matter i that the composition may be indicated in the following manner:

'CzH4OOC.R' .C0O]R' in which the characters have their previous-significance and'a: is a relatively small whole number e less than 1'0, and probably less than 5;. and in the lution in water, and usually in the presence of monomeric form at, of course, is l. The limitations on the size of :c are probably influenced largely by the fact that reaction leading to further growth is dependent upon random contact. Some of the products are self-emulsifiable oils, or self-emulsifiable :compounds; whereas, others give cloudysolutions or sols; and the most desirable type is characterized-by giving .a clear sosoluble calcium or magnesium salts, and frequently, in the presence of significant amounts of either acids or alkalies. I

Water solubility can be enhanced in.a number of ways which have been suggested by previous manufacturing directions, forinstance:

(a) By using a more highly polymerized ethyl- 'eneglycol; I

(b) By using a polymeric form instead-of a monomeric form in regard to theunit which 1 1,

forms thechain between the two alcoholic (b) By using a polybasic carboxy acid of'lower molecular weight, for instance, maleic acid, in

stead of adipic acid;

(d) By using'an alcoholic ricinoleo'amide, instead of the substituted amide of a wax acid of higher molecular acid.

'Inany event, it is to be noted that the -compounds of the type herein contemplated are lim- 1 ited to the'water-soluble type, i. 'e., those which are self-emulsifying in water or produce a sol or a molecular solution. x

material of lower molecular weight, for instance, "a substituted -water-repellent textile finish, etc.

Actually, a reaction involving an alcohol and an acid (esterification) may permit small amounts of either one or both of,the reactants,

moved by any suitable base, for instance, ammonia, triethanolamine, or the like, especially in dilute solution, Naturall precaution should be taken so that neutralization takes place without saponification or decomposition of the ester. In somecases there is no objection to the presence of the acidic group. Instead, if a tribasic acid be employed in such a manner as to leave one free carboxyl group, then it is usually desirable to neutralize such group by means of a suitable basic material.

In the hereto appended claims, reference to a neutral product refers to one in which free car'- boxylic radicals are absent.

Materials of the kindfherein contemplated may find uses as wetting, detergent, and leveling agents in the laundry, textile, and dyeing-industry; as wetting agents and detergents in the acid washing of fruit, in the acid washing of building stone and brick; as a wetting agent andspreaderin the application of asphal in road building and the like, as a constituen of soldering flux preparations; as a flotation reagent in the flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifiers for cosmetics, spray oils,

These uses are by nomeans exhaustive.

However, the most important phase of the present invention, as far as industrial application goes, is concerned with the use of the matecompounds or reagents herein described, and particularly desirable .for use as demulsifiers, may also be used for other purposes, for instance, as

a breakinducer in doctor treatment of the kind intended to sweeten gasoline. SeeU. S. Patent No. 2,157,223, dated May 9, 19 39, to Sutton.

Chemical. compounds of the kind herein described are also of value as surface tensiondepressants in the acidization of calcareous oil- 'bearing strata by means of strong mineral acid,

such as hydrochloric acid. Similarly, some members are effective as surface tension depressants or wetting agents in the flooding of exhausted oil-bearing strata. I As to using compounds of the kind herein described as flooding agents forrecoverinsoilfrom ventional procedure, so as to give a substantially neutral product. The introduction of such low contemplated, any residual acidity can be remolal hydrophobe groups does not seriously affect the solubility, and in some instances, gives increased resistance, to soluble calcium and'magnesium salts, for such property is of particular value. Usually, however, neutralization with a dilute solution ofammonia or the .likejis just as practicable and less expensive.

- What has just been said,can be recapitulated and presented in more formal agreement with customary nomenclature the following maner: As stated previously; in the broadest aspect,

the polyalkylene glyools employed may be indicated by the following formula:

v omcnrraomrr in which m has. its previous significance, and n represents a numeral varying from '2 to 4. In

' simpler form, this structure canbe'indicated in the following manner:

. Home-0H 1 in which the divalent radical RO is the diva: lent radical CnH:2nO) mas previously defined. The dibasic acid, previously referred to,' in its simplest form as HOOC.R".COO.H, is more 'completely portrayed by the following formula:

' coon a.-:.-0Q

doom ,1 in which R1 is the polybasic carl'ioxy acid residue,

except in the unique case of oxalic, and n. is the numeral 0 or 1, depending-uponwhether or not the polybasic acid is dibasicor tribasic.

\ If the polybasic acid just described is'indicated by R, and if the glycol just described is indicated by R",-then the acidic or fractional ester, presubterranean strata, reference is made to the procedure described in detail mu 8. Patent No? 2,226,119, dated December-'24. 1940, to De Groote and Kaiser. As to'using compounds of the kind hereimdescribed as. demulsifiers, or ii1 particular .as surfacetension depressants, in combination.

I with mineral acid or acidization .of.oil-bearing strata, reference ismade'to U. S. Patent No.

2,233,383, dated' -February 25, 1941; De Groote andKeiser. J

It will be apparent to those skilled in"the"art that residual carboxyl acidity can bev eliminatedv viously described in the specification, may be indicated by the following formula;

I [M [tain which '11 and 1) represent numerals. varying from I to '10, and 4)" represents a'numeral vary-- ing from -1 to 20, and R and R" have their prior significance, and theiratio'ofp to p varies from 1 2:1 to p-ilzp', with the obvious-proviso-that such 1 I ester must contain atleast two free carboxyl radicals.

Previous reference has been made to the hydroxylated compound, which .is a water-soluble detergent-forming monocarboxy acid amide-of 8 andnot over 32 carbon atoms and R; is 9.1118111? ber of the class consisting of. alkanol radicals',

and alkyleneoxyalkanol radicals; R4 is a hydrocarbon r'adical having not over 18 carbon atoms;'

acylradicalof the aforem'-"- represents a numeral varying from ,0 to 1,.

and n"'.represents a numeral varying from 1 to 2, with the proviso that m' "-and 12, plus m,

must equal 2.

It has been previously pointed out that such an .amide, particularly obtained by'th action of glycid, may have. as-"many as 6 reactive hydroxyl by esterification with 'a' low molal alcohol, for.

instance, ethy'l, methyLor 'propyl alcohol, by con radicals. In' other instances, there may be only a single alcoholic-hydroxyl radical. Thus, the

indicated by the formula; I Ramp-1w in which R may be considered as the residual part of the hydroxyl amide, usually the hydroxyl radicals themselves. As previously pointed out,

1 hydroxylated amide herein contemplated maybe in its complete aspect, such amide is characterv ized by the formula:

in which the divalent radical R0 is the divalent radical'(CnHznO)m in which radical, in

turn, 1:. represents a numeralvarying from 2 to 4,

' hydrogen atom, and n is the numeral 0 to 1;

in which ReCO is the acyl radical and R2 and R."-

, have their previous significance.v Subsequently,

in recapitulating the formula, in order 'to preserve the differences between various radicals,

RiCO will be referred to as R100.

As presented, the new composition of matter herein contemplated is suitably portrayed as an ester obtained by the esterification reaction 'involving the acidic fractional ester above described, and the hydroxylated amide previously depicted in detail. The final composition may be obtained in any suitable manner, and would properly represent the final product, regardless of the. intermediate steps. So portrayed,

the structural formula is asfollowsz, 1 I

[Mia in which all of the characters have their prior significance, and m represents a numeral from 1 to 6, m'represents a numeral from 1 to 3, and

171." represents a numeral varying from 1 to '6.

It has been previously pointed out that'in re,- sidual carboxylicradicals, andespecially'one obtained from tribasic acids, it could be neutralized with a variety .of suitable basic materials. In

other words, a residual carboxylic hydrogen atom" may be replaced bya metallic atom, an ammonium radical, or substituted ammonium radical,

as vpreviously indicated. Under such circumstances, any residual carboxylic radical, instead of appearing thus: COOH, may, inessence, be

1 the radical CQORe, in which Re represents a cation including the acidic hydrogen atom,

This can best. be disposed of by rewriting the 1 formula for the polybasic carboxy acid,thu's:.

coon

- 000m). in which all ofthe characters havetheir-previous significance.

R2(0H)n" is an abbreviated form of the amide of the form'ula: l

v i- R'IC ONQBal- [Bil-v" in which Rico is the acyl radical of the aforementioned monocarboxy' acid and having at least 8 and not over 32 carbon atoms, and R3 is a member of the class consisting of alkanol radicals, and alkyieneoxyalkanol radicals; R4 is a hydrocarbon radical having not over 6 carbon atoms; m represents a numeral varying from 0 to 1, and n represents a numeral varying from 1 to 2, with theprovisothat m' and n', plus m, must equal 2.

2, The ester, as defined in claim 1, wherein n is zero.

3. The ester, as defined in claim 1, wherein n is zero and m is zero.

4. The ester, as defined in claim 1, wherein n is zero, m""is zero, and .nrepresents the numeral2. v

5, The ester, as defined in claim 1, wherein n is zero, m' is zero, n represents the numeral 2,

and 111. represents a numeral varying from 7 to 11..

6. The ester, as defined in claim 1, wherein n is zero, m' is zero, 11. represents the numeral 2, m represents a numeral varying from 7 to 11, and Rico is the acyl radical of a higherfatty acid having 18carbon atoms.

7.. The ester, as defined in claim 1, wherein n is zero, m" iszero, n represents the numeral 2, m

represents a numeral varying from '7 to .11, and

R100 is the acyl radical of a higher fatty acid having 18 carbon atoms and an ethylene'linkage.

8. The ester, as defined in claim 1, wherein n is zero, m' is zero, n represents the numeral 2, m

' represents a. numeral varying from 7 to 11, and

. is zero, m is zero, n represents the numeral 2, m

Having thus described'our invention, what we claim as new and desire to secure by Letters Patent is:

1. A water-soluble ester of the formula:

represents the numeral 1 to 3, and m" represents the numeral froml to 6; and in which 12 and p represent numerals varying from 1' to 10, and

the ratio of p to p varies from 2:1to p+1:'p, and p"- represents a numeral varying from 1 to 20, and R is a glycol of the formula HO ROH,

in which m represents the numeral 1 to 6, m

R-zCO is the acyl radical of a higher fatty acid having 18 carbon atoms and an ethylene linkage,

and the ratio of 11 top is 2to 1.

9. The ester, as defined in claim 1,,whereihn' represents a numeral varying from 7 to 11, R-zCO is the acyl radical of a higher fatty acid havin 18 carbonatoms and an ethylene linkage; the ratio of p to p is 2 to -1, and --with added neutralization of all residual acidity.

10. The ester, as defined in claim 1, wherein 'n'.

is zero, m is zero, n represents the numeral 2, m

represents a numeral varying from 7 to 1, and R'zCO is the acyl radical of a higher fatty acid having 18 carbon atoms and an ethylene linkage; the ratio of p to p is 2 to 1, andwith the added neutralization of all residual acidity; an'd R1 is an adipicacidresidue. Y

11. The ester, as defined in claim 1, wherein n is zero, m is zero, 11. represents the numeral, 2, m represents-a numeral varying from 7 to 11, and R'zCO is the acyl radical of a higher fatty acid having 18 carbon atoms and an ethylene linkage;

the ratio of p to p is 2 to 1, and with the added 12. The ester, as defined in claim 1, wherein n the ratio of p to p is 2 to 1, and with the added neutralization of all residual acidity; and R1 is a maleic acid residue.

- neutralization of all residual acidity; and R is a -succinic acid residue.

13. In the method of manufacturing a water- I soluble ester, as defined in claim 1, the steps of:

'(A)' Esterifying a polyalkylene glycol having at least 7 and not more than 1'1 ether linkages; and

in which the alkylene radical thereof contains at least 2 and not more than 6 carbon'atoms with a polycarboxy acid having not over 6 carbon atoms,

the ratio of esteritying reactants being within the range of 1 mole and not over 2 moles of the polycarboxy acid for each mole of the polyalkylene glycol, so as to yield an acidic fractional ester having at least 2 unreacted carboxyl radicals; and

(B) Esterifying said acidic fractional ester-with av water-insoluble detergent-forming acid amide having an acyl radical containing more than 8 and not more than 32 carbon atoms and having a substituted amide radical in which at least one alcoholiform hydrocarbon radical is a substituent for an amino hydrogen atom; the ratio of reactants being 2 moles of the hydroxylated amide for each mole of the-acidic fractional ester.

' MELVDPDE GROOTE.

BERNHARD KEISER. 

